US6720392B2 - Aqueous amino resin blends - Google Patents

Aqueous amino resin blends Download PDF

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US6720392B2
US6720392B2 US10/139,476 US13947602A US6720392B2 US 6720392 B2 US6720392 B2 US 6720392B2 US 13947602 A US13947602 A US 13947602A US 6720392 B2 US6720392 B2 US 6720392B2
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amino
mol
amino resin
mass
formaldehyde
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US20030065133A1 (en
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Frank Scholl
Johann Wonner
Wolfgang Scholz
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Ineos Americas LLC
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Solutia Germany GmbH and Co KG
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Assigned to CYTEC SURFACE SPECIALTIES GERMANY GMBH & CO. KG reassignment CYTEC SURFACE SPECIALTIES GERMANY GMBH & CO. KG CORRECTING ADDRESS OF RECEIVING PARTY AT R/F 017946/0967 Assignors: SURFACE SPECIALTIES GERMANY GMBH & CO. KG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/40—Chemically modified polycondensates
    • C08G12/42—Chemically modified polycondensates by etherifying
    • C08G12/421—Chemically modified polycondensates by etherifying of polycondensates based on acyclic or carbocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/40—Chemically modified polycondensates
    • C08G12/42—Chemically modified polycondensates by etherifying
    • C08G12/424—Chemically modified polycondensates by etherifying of polycondensates based on heterocyclic compounds
    • C08G12/425—Chemically modified polycondensates by etherifying of polycondensates based on heterocyclic compounds based on triazines
    • C08G12/427—Melamine
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C09D161/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C09D161/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine

Definitions

  • the present invention relates to aqueous amino resin blends comprising as additives aliphatic amines containing at least one amino group and at least one hydroxyl group, the use thereof as impregnating resins, and a process for the reduction of the formaldehyde emission from impregnates by adding such amines to amino resins.
  • woodbase materials are coated using coated foils (finished foils) and impregnated cardboards (edgings), respectively (Kunststoff-Handbuch vol. 10, Duroplaste [Thermosets], Hanser-Verlag, 2 nd ed. 1988, p. 464 f., pp. 477 to 479).
  • thermosets such as urea-formaldehyde and/or melamine-formaldehyde resins, for example, in combination where appropriate with aqueous dispersions of thermoplastic resins such as acrylic dispersions or styrene-acrylic dispersions, drying the coated papers in a stream of hot air and at the same time curing the resins, and then coating the impregnated or resinated papers.
  • amino resins thermosets
  • thermoplastic resins such as acrylic dispersions or styrene-acrylic dispersions
  • Adequate penetration of the impregnation liquors into the paper is achieved if the resin solution is processed from aqueous or alcoholic dilution. Owing to the high level of cellulose swelling in aqueous systems, the foils and edgings produced from high aqueous dilution are brittle, exhibit a high level of water absorption, and even in the coated state have a surface whose aesthetic appeal is low.
  • the procedure described in DE-A 23 09 334 which uses impregnating liquors diluted with C 1 to C 4 alcohols, does give foils and edgings having good performance properties but requires cumbersome measures for reprocessing the waste air.
  • non-etherified urea-formaldehyde resins which have a mass fraction of melamine in the finished resin of from 1 to 5%, the reaction mixture being neutralized, following complete condensation, by the addition of specific tertiary hydroxyalkylamines (preferably triethanolamine, methyldiethanolamine, and dimethylethanolamine). These resins are used as impregnating resins. There is no reporting of the advantageous effect of (hydroxyalkyl)amines on the reduction of formaldehyde emissions from finished foils and edgings.
  • Formaldehyde emissions of ready-produced finished foils and edgings are determined following storage under standard climatic conditions (23° C., 50% relative humidity) in accordance with the standard EN 717-2 (FESYP method, gas analysis). Foils and edgings with formaldehyde emission values of less than 3.6 mg/(h ⁇ m 2 ) by the FESYP method comply with the limit (“E 1”) and are referred to below as E1 edgings. The rates of emission found remain more or less constant even after several weeks of storage under standard conditions.
  • Emissions of formaldehyde are due to the use of urea-formaldehyde and/or melamine-formaldehyde resins in the liquors for impregnating the paper or cardboard sheets and/or in the formulations for coating the foils and edgings.
  • urea-formaldehyde and/or melamine-formaldehyde resins in the liquors for impregnating the paper or cardboard sheets and/or in the formulations for coating the foils and edgings.
  • mixtures of organic hydroxy compounds and an amide are suitable for use as formaldehyde-binding agents in boards made from wood cellulose materials.
  • the use of these mixtures as formaldehyde scavengers in finished foils and edgings is not described.
  • Addition of the mixtures described in DE-A 34 03 136 to amino resins that are used to produce finished foils and edgings leads to a marked deterioration in the flexibility of the finished foils and edgings produced with them.
  • aqueous amino resin blends which comprise as additives, aliphatic linear, branched or cyclic amines containing hydroxyl groups.
  • This invention therefore relates to a process of reducing the formaldehyde emission from finished foils and edgings, wherein aqueous amino resin blends are used for impregnation which comprise aliphatic linear, branched or cyclic amines A having at least one amino group which may be primary, secondary or tertiary, at least one hydroxyl group and from 2 to 20 carbon atoms, and non-etherified or at least partly etherified amino resins B.
  • the present invention also relates to a method of use of amines A having at least one amino group that may be primary, secondary or tertiary, one hydroxyl group and 2 to 20 carbon atoms, comprising adding these amines A to amino resins, and impregnating paper or cardboard with such modified amino resins to reduce formaldehyde emissions from the impregnates.
  • the invention also relates to an aqueous amino resin blend
  • an aqueous amino resin blend comprising aliphatic linear, branched or cyclic amines A having at least one amino group which may be primary, secondary or tertiary, at least one hydroxyl group, and 2 to 20 carbon atoms, and non-etherified or at least partly etherified amino resins B, wherein the amino resins have a mass fraction of melamine of less than 1% or more than 5%, in the case where the amines A comprise tertiary hydroxyalkylamines. It is preferred in this case, that the mass fraction of melamine in the amino resins is at least 7%, particularly preferably at least 10%; or at most 0.9%, particularly preferably at most 0.75%, and especially preferably at most 0.5%.
  • the invention also relates to an aqueous amino resin blend comprising aliphatic linear, branched or cyclic amines A having at least one amino group which may be primary, secondary or tertiary, at least one hydroxyl group, and from 2 to 20 carbon atoms, and at least partly etherified amino resins B.
  • the present invention also relates to a method of use of the aqueous amino resin blends in the production of finished foils or edgings, comprising impregnating paper or cardboard with the said amino resin blends, and subsequently drying the impregnates.
  • the amines A have preferably from 4 to 12 carbon atoms.
  • the number of hydroxyl groups in the amines A is preferably at least equal to the number of primary, secondary or tertiary amino groups.
  • Suitable amines A are preferably selected from the group consisting of ethanolamine, diethanolamine, bis-2-hydroxypropylamine, bis-3-hydroxypropylamine, triethanolamine, tris-2-hydroxypropylamine, N-methylethanolamine, N-benzylethanolamine, N,N-dimethylethanolamine, 2-hydroxyethylpiperazine, bis-2-hydroxyethylpiperazine, N,N′-bis(2-hydroxyethyl)diaminoethane, and N,N,N′,N′-tetrakis(2-hydroxyethyl)diaminoethane.
  • the amines A contain secondary and/or tertiary amino groups, particularly preferably exclusively secondary and/or tertiary amino groups. It is especially preferred that the amines have exclusively secondary amino groups and in particular, the number of hydroxyl groups of these amines is greater by at least 1 than the number of secondary amino groups.
  • Such amines are diethanolamine, bis-2-hydroxypropylamine, bis-3-hydroxypropylamine, N-methylethanolamine, N-benzylethanolamine, 2-hydroxyethylpiperazine, and N,N′-bis(2-hydroxyethyl)diaminoethane.
  • the amino resins B are water-soluble melamine-formaldehyde resins, urea-formaldehyde resins or mixed melamine-urea condensates which are non-etherified or at least partly etherified with aliphatic linear or branched alcohols, in particular with C 1 to C 4 alcohols.
  • the expression “at least partly etherified” here means that at least 10% of the groups originating from the addition of formaldehyde onto the amino resin former (methylol groups, N-methylene groups and alkoxymethyl groups) are present in the form of alkoxymethyl groups.
  • compositions of the invention it is also possible to use those melamine resins in which a fraction (up to 20% of their mass) of the melamine has been replaced by other aminotriazines such as acetoguanamine, caprinoguanamine or benzoguanamine.
  • Preferred resins contain less than 10%, in particular less than 5%, measured on the same scale, of aminotriazines which are different from melamine.
  • the amount of substance of aminotriazines, divided by the sum of the amounts of substance of aminotriazines and urea, is from 0 to 1 mol/mol.
  • the content of bonded formaldehyde per each —NH 2 group in the amino resins B, expressed as the ratio of the amount of substance of N-methylol groups and the sum of the amounts of substance of free and of (singly or doubly) methylolated amino groups, is from 0.5 to 2.0 mol/mol, preferably from 0.55 to 1.95 mol/mol, and particularly preferred from 0.6 to 1.9 mol/mol.
  • the content of alkoxy groups originating from the etherifying alcohol is from 0.0 to 2.0 mol/mol, preferably from 0.1 to 1.95 mol/mol, and particularly preferred from 0.15 to 1.9 mol/mol.
  • the resins are at least partly etherified with the aforementioned alcohols, especially methanol, ethanol, n-butanol and isobutanol. Particular preference is given to methanol-etherified amino resins.
  • the preparation of the amino resins B is widely known. First of all, methylolation and condensation are carried out by adding amino resin formers (melamine, urea, the abovementioned other aminotriazines where appropriate) to formaldehyde at a pH of from 7 to 10 and a temperature of from 40 to 110° C., after which the etherifying alcohol is optionally added and reaction is optionally continued at a pH from 1 to 7 and at a temperature from 30 to 80° C.
  • the condensation and etherification conditions are guided by the level of water dilutability that is desired for the resin, which is at least 1 part by weight resin to 5 parts by weight deionized water, and by the required penetration properties.
  • the amino resin blends of the invention may further comprise additives, especially polyethylene glycols C1 and/or aqueous dispersions of a copolymer C2 which preferably contains a mass fraction of at least 50% of units derived from (hydroxy)alkyl (meth)acrylates and/or (meth)acrylic acid.
  • (Hydroxy)Alkyl (meth)acrylates are meant to include, in this context, hydroxyalkyl methacrylates, hydroxyalkyl acrylates, alkyl methacrylates and alkyl acrylates.
  • urea 0.5 to 5 cg/g which is equivalent to 0.5 to 5 g/(100 g)
  • polyfunctional alcohols containing from 3 to 6 hydroxyl groups such as trimethylolpropane, erythritol, pentaerythritol, dimethylolpropane, dipentaerythritol, xylitol, sorbitol and mannitol (0.5 to 7 cg/g which is equivalent to 0.5 to 7 g/(100 g)), have proven advantageous.
  • the stated amount for addition is in each case the mass of the addition based on 100 g of the (undiluted) amino resin. As these additives are added after the condensation of the amino resin, they are not incorporated into the condensation resin.
  • Suitable polyethylene glycols C1 are oligomers or polymers having (number-average) molar masses M n of up to about 2000 g/mol. Preference is given to liquid polyethylene glycols having molar masses M n of from 200 to 600 g/mol. They are used where appropriate in amounts such that the ratio of the mass of C1 to the mass of the solids fraction in the solution or dispersion of the amino resin is between 5 and 50 g/(100 g), preferably from 15 to 45 g/(100 g).
  • the copolymer dispersions C2 are dispersions of acrylic copolymers in water, preparable for example by emulsion copolymerization of olefinically unsaturated monomers, the monomer mixture used to prepare them preferably containing a predominant fraction (more than 50% of its mass) of acrylic monomers, i.e., acrylic or methacrylic acid and derivatives thereof, especially esters with aliphatic alcohols having from 1 to 10 carbon atoms, and esters with aliphatic polyhydroxy compounds having from 2 to 10 carbon atoms and at least two hydroxyl groups per molecule.
  • acrylic monomers i.e., acrylic or methacrylic acid and derivatives thereof, especially esters with aliphatic alcohols having from 1 to 10 carbon atoms, and esters with aliphatic polyhydroxy compounds having from 2 to 10 carbon atoms and at least two hydroxyl groups per molecule.
  • Preferred acrylic monomers among the esters are methyl, ethyl, n-butyl, t-butyl, hexyl and 2-ethylhexyl (meth)acrylate, hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate.
  • the ratio of the mass of copolymer in the copolymer dispersion C2 to the mass of the amino resin B in its aqueous solution or dispersion can be (5 to 150 g): 100 g, preferably (20 to 140 g): 100 g, in the composition.
  • the finished foils and edgings produced using the amino resin blends of the invention are distinguished by up to 90% reductions in formaldehyde emission under standard and tropical conditions as compared with the prior art.
  • the performance properties of the amino resin blends, and the properties of the finished foils and edgings so produced, are otherwise equivalent to those of the prior art.
  • Each impregnation liquor was adjusted to a mass fraction of solids (nonvolatiles content, NVC) of 75% (measured as the dry residue after drying at 120° C. for 1 h in a small glass dish) by adding DI (fully deionized) water.
  • NVC nonvolatiles content
  • These resin liquors were applied to papers by knife coating with a mass per unit area of approximately 200 g/m 2 (typical edgebanding cardboard) and the impregnated papers were then dried at 180° C. (in a forced air oven) for 90 seconds.
  • the resin addon was 38 to 42% (mass of solid resin based on the mass of the dry paper before impregnation).
  • samples of the impregnated paper were conditioned for 3 days under standard conditions (23° C., 50% relative humidity) prior to each measurement.
  • the edging samples were stored at 35° C. and 90% relative humidity for 1 week, and were also reconditioned for 3 days in each case under standard conditions prior to the actual measurement.
  • the formaldehyde emissions (F emissions) were measured in accordance with EN 717-2.
  • the performance suitability of the resin blends was tested.
  • the pot life is the time taken for an impregnation liquor stored at 30° C. to attain a viscosity (measured as the flow time from a 4 mm cup, DIN 53211, at 23° C.) of more than 60 s or for the penetration time with a defined test paper to have risen to more than 70 s.
  • the flexibility of the edgings was assessed by means of the bending test at room temperature. The parameter stated is the bending radius at which the edge still just does not break.
  • the split resistance is a measure of the strength of the impregnated edging after the resin is cured.
  • the resin addon was 27 to 29% (mass of solid resin based on the mass of the dry paper before impregnation).
  • a commercial acid-curing paint (Treffert GmbH, grade 136-07, together with curing agent 176-01; on the basis of aqueous polyols with amino resins) was then applied to the impregnated paper with a doctor blade, the loading being up to 14 g/m 2 , and dried at 155 to 160° C.
  • the resin solution had a mass fraction of solids of 74.6%, a pH of 9.7, a mass fraction of free formaldehyde of 0.7%, the viscosity as measured at 23° C. was 125 mPa ⁇ s. According to 13 C NMR measurement, the ratio n C :n F :n MeO of amounts of substance of urea, bonded formaldehyde, and methoxy groups was 1 mol:1.94 mol:1.58 mol.
  • each impregnation solution was set to a mass fraction of solids (nonvolatiles) of 75% (as determined by drying at 120° C. for 1 hour in a glass dish).
  • These impregnating liquors were applied to paper having a mass by unit area of 200 g/m 2 (usual edging cardboard) with a doctor blade, the impregnated paper was dried for 90 seconds at 180° C. in a convection oven.
  • the resin addon was 38 to 42% (mass of solid resin per mass of dry unimpregnated paper).
  • the edging samples were conditioned for 3 days in standard conditions (23° C., 50% relative humidity).
  • Formaldehyde emission was determined according to the EN 717-2 standard.
  • Formaldehyde emission values listed in table 4 are averages of the values for 1 hour until 4 hours.
  • the effect of the amines in reduction of formaldehyde emission can be clearly seen.
  • the secondary amine, DEA is more effective than the tertiary amine, TEA.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)
US10/139,476 2001-05-17 2002-05-06 Aqueous amino resin blends Expired - Fee Related US6720392B2 (en)

Applications Claiming Priority (3)

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DE10123948.3 2001-05-17
DE10123948 2001-05-17
DE10123948 2001-05-17

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US (1) US6720392B2 (pl)
EP (1) EP1258512B1 (pl)
AR (1) AR033727A1 (pl)
AT (1) ATE342315T1 (pl)
BR (1) BR0201853A (pl)
CA (1) CA2386667A1 (pl)
DE (1) DE50208378D1 (pl)
ES (1) ES2273942T3 (pl)
MX (1) MXPA02004918A (pl)
NO (1) NO328524B1 (pl)
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DE10245960A1 (de) * 2002-10-02 2004-04-15 Creavis Gesellschaft Für Technologie Und Innovation Mbh Polykondensationsharze mit aminfunktionalisierten Polymeren
CN106634288A (zh) * 2016-09-22 2017-05-10 佛山市美联涂料有限公司 水性工业烤漆
CN117106395A (zh) * 2022-05-17 2023-11-24 浙江福莱新材料股份有限公司 大飞机用超声融合胶及其制备工艺

Citations (13)

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Publication number Priority date Publication date Assignee Title
US3352838A (en) 1963-12-12 1967-11-14 Ciba Ltd Methylolated urea and melamine etherified with butanol and polyethyleneglycol as emulsion polymerization agents
DE2309334A1 (de) 1973-02-24 1974-08-29 Cassella Farbwerke Mainkur Ag Verfahren zur herstellung von melaminharzfolien
JPS555967A (en) 1978-06-29 1980-01-17 Hitachi Chem Co Ltd Amino resin composition
JPS55149342A (en) 1979-05-11 1980-11-20 Mitsui Toatsu Chem Inc Aminoplast resin with improved stability
US4374899A (en) 1980-05-19 1983-02-22 Reichhold Chemicals, Incorporated Hardboard treating composition and process for forming hardboard surfaces
DE3403136A1 (de) 1983-02-07 1984-08-09 Enigma N.V., Curacao, Niederländische Antillen Formaldehydbindendes mittel
US4713299A (en) 1985-03-05 1987-12-15 Formica Corporation Modified melamine resin for use in decorative laminates
WO1988006176A1 (fr) 1987-02-19 1988-08-25 Basf Lacke + Farben Aktiengesellschaft Laque aqueuse a deux composants de revetement a couche unique de pellicules de finition et de bords continus de haute resistance
DE3837965A1 (de) 1988-11-09 1990-05-17 Basf Ag Hitzehaertbare, waessrige kunstharz-mischungen zur beschichtung von holzwerkstoffen
DE4439156A1 (de) 1994-11-04 1996-05-09 Cassella Ag Tränkharze für Folien und Kanten
EP0913412A1 (fr) 1997-10-31 1999-05-06 Elf Atochem S.A. Procédé de préparation de résines thermodurcissables urée-formol dopées à la mélamine et utilisation de ces résines en tant que résines d'imprégnation
DE19835114A1 (de) 1998-08-04 2000-02-10 Basf Ag Mikrokapseln aus formaldehydarmen Melamin-Formaldehydharzen
EP1152043A2 (de) 2000-05-05 2001-11-07 Solutia Germany GmbH & Co. KG Aminoharzgemisch zur Herstellung von Folien und Kanten mit reduzierter Formaldehydabspaltung

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3352838A (en) 1963-12-12 1967-11-14 Ciba Ltd Methylolated urea and melamine etherified with butanol and polyethyleneglycol as emulsion polymerization agents
DE2309334A1 (de) 1973-02-24 1974-08-29 Cassella Farbwerke Mainkur Ag Verfahren zur herstellung von melaminharzfolien
JPS555967A (en) 1978-06-29 1980-01-17 Hitachi Chem Co Ltd Amino resin composition
JPS55149342A (en) 1979-05-11 1980-11-20 Mitsui Toatsu Chem Inc Aminoplast resin with improved stability
US4374899A (en) 1980-05-19 1983-02-22 Reichhold Chemicals, Incorporated Hardboard treating composition and process for forming hardboard surfaces
DE3403136A1 (de) 1983-02-07 1984-08-09 Enigma N.V., Curacao, Niederländische Antillen Formaldehydbindendes mittel
US4713299A (en) 1985-03-05 1987-12-15 Formica Corporation Modified melamine resin for use in decorative laminates
US4940841A (en) 1987-02-19 1990-07-10 Basf Lacke & Farben Aktiengesellschaft Aqueous two-component paints for one-coating of high-resistant finishing sheeting and continuous edging
WO1988006176A1 (fr) 1987-02-19 1988-08-25 Basf Lacke + Farben Aktiengesellschaft Laque aqueuse a deux composants de revetement a couche unique de pellicules de finition et de bords continus de haute resistance
DE3837965A1 (de) 1988-11-09 1990-05-17 Basf Ag Hitzehaertbare, waessrige kunstharz-mischungen zur beschichtung von holzwerkstoffen
DE4439156A1 (de) 1994-11-04 1996-05-09 Cassella Ag Tränkharze für Folien und Kanten
EP0913412A1 (fr) 1997-10-31 1999-05-06 Elf Atochem S.A. Procédé de préparation de résines thermodurcissables urée-formol dopées à la mélamine et utilisation de ces résines en tant que résines d'imprégnation
DE19835114A1 (de) 1998-08-04 2000-02-10 Basf Ag Mikrokapseln aus formaldehydarmen Melamin-Formaldehydharzen
US6261483B1 (en) 1998-08-04 2001-07-17 Basf Aktiengesellschaft Microcapsules of low-formaldehyde melamine/formaldehyde resins
EP1152043A2 (de) 2000-05-05 2001-11-07 Solutia Germany GmbH & Co. KG Aminoharzgemisch zur Herstellung von Folien und Kanten mit reduzierter Formaldehydabspaltung
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EP1258512B1 (de) 2006-10-11
ATE342315T1 (de) 2006-11-15
CA2386667A1 (en) 2002-11-17
EP1258512A1 (de) 2002-11-20
US20030065133A1 (en) 2003-04-03
BR0201853A (pt) 2004-04-13
AR033727A1 (es) 2004-01-07
PL205284B1 (pl) 2010-03-31
DE50208378D1 (de) 2006-11-23
ES2273942T3 (es) 2007-05-16
PL353949A1 (en) 2002-11-18

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